DE1669277A1 - Water-compatible crosslinking agents for reactive polymers and mixtures of substances produced with them - Google Patents

Description

Dr. MEDlGER

Water-compatible crosslinking agents for reactive polymers and thus manufactured mixtures of substances

The invention "relates to improved aqueous compositions for Production of heat-hardenable impregnations and coating layers. In particular, the object was to provide improved water-dilutable aqueous solutions of N-methylol condensates organic polycarboxamides, especially the diamides and triamides, to accomplish.

The invention is based on the use of methyl-coated polycarboxamides as a crosslinking additive to such polymers capable of reacting with the methylolpolycarboxamides mentioned are. The invention relates to mixtures consisting of:

A. an aqueous dispersion of a water-insoluble emulsion copolymer composed of monoethylenically unsaturated Monomers, including 3 to 40 percent by weight of at least one monomer, the alcoholic hydroxyl, Contains ureido or garboxylamide groups,

B. 1 to 20%, calculated on the weight of the co-polymer, a methylolated polycarboxamide that is compatible with water. ·

As a hydroxyl group-containing comonomer of the water-insoluble one Any monomer which contains a vinylidene group HpC * C = and an oxyalkyl group is suitable for the emulsion copolymer. Examples are 2-hydroxyethyl acrylate, methyl alpha- (hydroxymethyl) acrylate, ethyl alpha ^ (hydroxymethyl) acrylate, butyl alpha (2-hydroxyethyl) acrylate, 2-hydroxypropyl acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate, methyl alpha- (2-hydroxypropyl) acrylate, Ethyl alpha- (3-hydroxypropyl) acrylate, 4-hydroxybutyl acrylate, 5-hydroxyamyl acrylate, 6-hydroxyhexyl acrylate, 7-hydroxyheptyl acrylate, 8-hydroxyoctylaorylate, 9 ~ hydroxynonyl acrylate, 10-hydroxydecyl acrylate, 2-hydroxyethyl methacrylate, 6-hydroxyhexyl methacrylate, 8-hydroxyoctyl methacrylate, 10-hydroxydecyl meth-

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acrylate, 3T-hydroxypropyl crotonate, 5-hydroxyamyl crotonate, 6-hydroxyhexyl crotonate, 7-hydroxyheptyl crotonate, 10-hydroxydecyl crotonate, Di'2-hydroxyethyl) maleate, di (4-hydroxybutyl) maleate, di- (6-hydroxy-Jb.exyl) maleate, Di (9-hydroxynonyl) maleate, di (2-hydroxyethyl) fumarate, Di (4-hydroxybutyl) fumarate, di (6-hydroxyhexyl) fuma'rat, di (10-hydroxydecyl) fumarate and the same.

The alkyl can additionally, also, other substituents, such as secondary hydroxyl groups, nitrile groups, halogen atoms and the like contain, such as 2,3-dihydroxypropyl acrylate, 3,5-dihydroxyamyl crotonate, 6, 10-dihydroxydecyl methacrylate, di-2,6-dihydroxyhexyl maleate, Di (2-chlO3? "- 7-hydroxyh.eptyl) fumarate.

In all hydroxyesters, the hydroxyl group of each hydroxylalkyl group is at least 2 carbon atoms away from the carbon atom of the adjacent carboxyl group in the ester. Further examples of such ionomers are the hydroxy ( GP-Gi o) ~ alkyl vinyl sulfides or ethers, which contain one or more hydroxyl groups in the molecule, such as β-hydroxyethyl vinyl ether or sulfide, β-hydroxypropyl vinyl ether or sulfide, HydroxyäthoxyätJiylvinyläther, 2,3-Dihydroxypropylvinyläther, 10-Hydroxydecylvinyläther or sulfide, 6-Hydroxyhexylvinyläther, also the N-Hydroxyalkylacrylamides and methacrylamides, which contain amide and hydroxyl groups at the same time, such as N- (2-hydroxyethyl) acrylamide.

Also suitable are all monomers that have a vinylidene group and a Ureido group of the formula r ». ' ■

¹ 2

contain, in which at least one of the substituents R, E, R a Represents hydrogen atom, while the remaining substituents Hydrogen atom, an alkyl or aryl group, or a cyclic one ureido group of the formula

'he

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can be, in which A is an alkylene group, preferably with 2 or 5 C atoms, of which at least S G atoms are in a chain between the nitrogen atoms. Examples are the compounds · of the following general formula I and -II: ^r ": ·

-A ¹ -NE-CG-U ^ _o

- ^A

Il

It means Y an oxygen atom, a sulfur atom or the

Group -CQKH-. Or -COO-; A is an alkyl group with 2 to 12 C atoms or an alkoxyalkyl group each with 2 to 4 C atoms

'' '3 · ■ ■

in AIkJIf ₅ R, E and B. have the meaning given above} η has.

the value 1 or 2.. .

The compounds der.Formel I include 2-ureidoethyl vinyl ether and sulfide, H (2-ureidoethyl) acr3rlamid and 2-ureidoethyl acrylate and methacrylate. Examples of compounds of the formula II are N, N'-ethylene urea-N-ethyl yinyl ether, and sulfide, U- (B- (U ¹ - ^ U "-ethylene urea) ethyl) acrylamide or methacrylamide, B- (U ₁ U ¹ -Athylenurarnstpff) ethyl acrylate or methacrylate and the corresponding thioureido compounds, λ,.

All monomers with a vinylid group are also suitable and an arboxylamide group whose nitrogen atom is at least a hydrogen carries. These co-monomers form amide groups Copolymers. For example, acrylamide, methacrylamide, itaconamide, itaconamic acid, maleamic acid, fumaramic acid, dte U-methylol derivatives difeser amides, the U-methyl bis

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! -butyl substituted derivatives of these amides, the Ef-ß-hydroxyethyl, - K-ß-hydroxypropyl, and other E-hydroxypropyl and If-hydroxy-butyi-substituted derivatives of the former Amides that. N-ethoxymethyl, if-butoxymethyl, N-ethoxyethyl, and other N-alkoxyalkyl substituted derivatives of the former Amides. Acrylamide, methacrylamide and itaconamide are preferred, which are expedient make up about 5 to 10 percent by weight of the copolymer.

In this invention, the term "amide" in relation to the Emulsion copolymer not only the ureido compounds that "can also be referred to as carbamide compounds, but also the carbonamide and carboxyamide compounds.

The monomers containing amide groups and / or hydroxyl groups can be capable of interpolymerization with one or more others Monomers are mixed polymerized, for example with the nitriles and esters of acrylic acid or methacrylic acid, which of the general formula III

III H ₂ C = C- (CH ₂ ) _{n- 1} H

COOH

in which η takes the value 1 or 2. The esters can those of benzyl alcohol or a saturated monohydric alcohol having 1 to 18 or more carbon atoms, including cyclohexanol, alkyl-substituted Cyclohexanols and alkanols with up to 18 or more, preferably 1 to 8 carbon atoms.

For example, methyl acrylate, methyl methacrylate, Ethyl acrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, Octadecyl acrylate, also vinyl esters, such as vinyl acetate, vinyl chloride, Vinylidene chloride, vinyl aromatic hydrocarbons with 8 to 16 carbon atoms »especially styrene and the vinyl toluene (o, m, ρ or mixtures), vinyl (C ^ -C ^) alkyl ethers, such as vinyl ethyl ether,

DR-MEDlGER

^^, such as vinyl methyl sulfide.

In general, those with the amide or hydroxyl-containing Components of copolymerized monomers are so hydrophobic that like the representatives mentioned »However, the monomer range can sch in addition to the amide or hydroxyl ester components, 1 to 10, preferably not more than 5, percent by weight of hydrophilic co-monomers contain. Acids such as acrylic acid, methacrylic acid, itaconic acid, and amines, like dimethylaminoethyl acrylate and H-Mmethylaminoäthylacrylamid '

and the same. ..; ™

The copolymers used to carry out the invention can by all known methods of emulsion mixing polymerization getting produced. "Preferably and for most of them Uses are said to have a high molecular weight, such as it is common for emulsion copolymers. But are suitable also copolymers of low molecular weights, such as by Addition of 0.1 to 3 percent by weight of suitable chain terminators can be obtained in the polymerization mixture. Examples of such chain terminators are dodecyl mercaptas and methylene chloride and tribromochloromethane. Those made for the invention Copolymer latices can have solids contents of up to 60% and more,. f

A suitable methylolated polyamide crosslinking agent is any stable, water-compatible condensation product which can be diluted with water and which is obtained by reacting formaldehyde or compounds releasing it in an acidic aqueous medium in excess with a polycarboxylic polyamide. The amides of aliphatic carboxylic acids with 2 to 10 carbon atoms or one of the three phthalic acids (q, p * m), such as malonamide, glutaramide, <* - -Methylglutaramid, .. Sue ßinamid, adipamide, o-phthalamide are particularly suitable , Isopiitlialamidi Triamid ^ as Nitrilot ^ ipropionamid NCCHgOHg-COllHg) ± ■

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and the Triamid, which.es through. Heating ammonia at 50 to 7O ⁰ C with the reduced trimer of ethyl acrylate under pressure is obtained. Excess formaldehyde means an amount of formaldehyde greater than 1 mole per nitrogen atom of the polyamide. If, therefore, 3 moles of formaldehyde are used per mole of diamide in the production of a methylolated diamide, the reaction mixture initially contains a 50 percent excess of formaldehyde; if 5 moles of formaldehyde are used, the excess is 67 % * Um 'stable dispersions of the methylolated polyamide To obtain, the formaldehyde excess should generally be at least 50 % and it can even be increased to 300 % and above, because there is apparently no upper critical limit. A dispersion is regarded as stable if, when stored in a closed container and under normal atmospheric conditions of the temperature, the solid substances contained therein neither gel nor crystallize out nor precipitate within a period of at least three months.

The simple di (F-methylol) -diamide or tri (li-methylol) -triamide may still be considered sufficiently water-soluble to act as a crosslinking agent to serve in the aqueous systems of emulsion polymers defined above. With the diaamids and some triamids with more than 4 carbon atoms, however, the water solubility is often correct limited or their aqueous solutions tend to be unstable and crystals of the methylolated amide to settle out if they are left for a day or a week. It was found that one. water-compatible aqueous dispersions methylolated Diamid © or Triamide obtained improved stability can with these higher amides, even if the dimethyloldiamide or dimethyloltriamide is practically insoluble in water by a considerable excess of photomaldehyde is used to form the methylolated condensate and this excess in the

resulting solution & ufrecht receives. That's how you put it: Diamond

or Tjjiamid in an acidic aqueous medium, for example

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a 37prozentigen formaldehyde solution containing 4 "to 6 moles of formaldehyde per mole of diamide or G to 7 moles of formaldehyde per mole triamide to the reaction may be from 40 to 11Q ⁰ C, preferably about 60 to 90 0, carried out in one to four hours until everything in the reaction medium has gone into solution. If you work at temperatures above about 95 to 96 ⁰ O, then we recommend the use of a pressure vessel *

Apparently, in the case of the diamide or triamide condensate, the reaction product is an equilibrium mixture of the N ₁ Ii '(dimethylol) derivative of the diamide or the JT * H *, li "-trimethylol derivative of the triamide, free formaldehyde, methylolated derivatives of the diamide or Triamides, which contain one or more groups -IT (H) (CHpO) _x H, in which χ can assume the value 1 or 2 yes even $ or 4, and possibly small amounts of a low condensation polymer of the above-mentioned methylolamide derivative, for example a dimer , Trimers, tetrameres, etc. In the total mixture, χ apparently has an average value between 1 and 2 «The preferred crosslinking agent is such an equilibrium mixture of methylated isophthalamide.

Any inorganic or organic acid is suitable to set the required pH value in the reaction mixture. For example, hydrochloric acid, sulfuric acid, oxalic acid, succinic acid, formic acid, acetic acid, etc. * are suitable. Usually one prefers formic acid »It has been found that strongly acidic conditions favor the Eondensationspolymerisation in the initial stage of the reaction with formaldehyde, so that the reaction does not stop when only the H ^ iP-dimethylol derivative of the diamide or the Η; _ν ϊϊ-, 3J "-trimethyloltriamide is formed. The condensate obtained under strongly acidic conditions can therefore be a pure monomer, dimer or trimer, but is generally apparently a mixture of 2 or more from the group of monomers, dimers, trimers , Tetramers, etc., so that the molecular weight of the condensate is an average of the various components of the mixture.

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Apart from that, you can go straight through. Implementation of the amide in an excess of at least 3 to 4, preferably 5 or 6 moles of formaldehyde per mole of amide, a stable solution of the methylolated Di- or triamide condensate can produce a stable Solution of the crosslinking agents of the invention also prepared by adding a lijN'-dimethyloldiamide in an aqueous solution of at least 1 to 2 moles of formaldehyde per mole of amide, preferably at least 3 moles of aldehyde per mole of amide. In the case of the trimethylo- ^ lated triamide, the formaldehyde solution should be at least 2 to 3 » preferably contain at least 4 moles of aldehyde per mole of amide.

In general, the solution of the methylolated amides in excess aqueous formaldehyde can have any concentration of the amide from 1 to 35 or 45 % or above. The maximum concentration depends on the particular methylolamide. Attempts to isolate the solid methylolamide component from the methylolated amide reaction product always have an N, N ¹ -dimethylol diamide or an N, Iv ¹ , W'-trimethylol triamide, depending on whether a diamide or a triainide Therefore, the information on the solids content or the content of methylolamide in the solution always refers to the content of dimethylolamide or trimethylolamide, even if this * component may not be partially or entirely in the Solution, but perhaps in the form of any compounds with the above-mentioned groups -N (H) (CH ₂ O) H. The chosen definition of the solids content excluding anhydrous formaldehyde is also justified by the fact that the titration of the free, ie unbound formaldehyde in these solutions of methylolated amides according to the customary sulfite method in each case all the formaldehyde except for 2 mol per mole of diamide or 3 moles per mole of triamide recorded.

The aqueous solution of the methylolated amide can therefore be referred to as' solution of the Η, Ν'-dimthylenediamide or the N, N ¹ , Ν '' - trimethyloltriamide and the concentration of the methylolated amide

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Specify condensate according to the calculated amount of M ", N'-dimethylol diamide or ΙΊ, Μ ¹ , H" -trimethylol triamide. For most practical purposes, the solutions of the crosslinking agents of the invention have methylolamide solids concentrations of about 25 to 45% or more, while the content of non-bonded formaldehyde titratable by the sulfite method is at least 1 to 2, preferably 3 moles in the jail of diamides and at least 2 to 3, preferably at least 4 moles in the case of a triamide per mole of methylolated amide. In order to keep these solutions stable, they will. stored in closed containers so that the evaporation of formaldehyde is prevented. The containers should only be opened briefly to remove partial quantities. A tap or a plug is expediently provided on the container in order to limit the escape of formaldehyde vapors to a minimum during removal.

The heat-curable polymer compositions are prepared by mixing the desired amount of the water-soluble methylolated dicarboxamide into the dispersion of the emulsion copolymer before or after the dispersion of the emulsion copolymer is adjusted to the concentration suitable for the application (about 1 to 30% or more, depending according to the needs of the individual case). The aqueous mixture of methylolated diamide and dispersed mixed polymer can be processed immediately after mixing or else first stored and / or shipped. Shortly before use, however, it is advisable to add a curing catalyst. As such, about 0.5 to 2% of an acid or an acid salt, calculated on the total weight of the aqueous mixture of substances, are suitable. Suitable catalysts of this type are, for example, hydrochlorides or other acidic salts of hydroxyaliphatic amines, for example 2-methyl-2-amino-1-propanol, 2-methyl-2-amino-1,3-propanol, 2-methyl-2-amino- 1,3-propanediol, tris (hydroxymethyl) aminomethane, 2-phenyl-2-amino-1,3-propanol, 2-methyl-2-amino-1-pentanol, 2-amiliobutanol, (β-piethanolamine, 2-amino-2 -ethyl-1-butanol, ammonium chloride, pyridine hydrochloride, benzyldimethylamine oxalate, the amine salts are water-soluble latent ones

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-ΙΟ catalysts that are practically neutral at normal temperature isind, but at the higher temperatures customary for curing to discrete volatile components, of which the one is angry. When heated, these catalysts initially exert their accelerating effect, but are subsequently used The course of the heating is automatically removed. The catalyzed mixtures of copolymers and crosslinking agents are suitable as adhesives or as impregnation and binding agents for textiles. For example, a nonwoven with such a mixture, which has a solids content of about 3 to 20 percent by weight, are impregnated. Compartment of The fibers of the non-woven fabric are permanently held together and the non-woven fabric can withstand the operations of the thermal treatment Are subjected to dry cleaning and washing.

In all applications, the aqueous dispersion of the invention has to be dried and hardened after application. Basically, it is sufficient to leave it at the normal temperature of the environment for a long time. However, the hardening is preferably accelerated by the action of heat, it being possible to go from tree temperatures up to 30O ⁰ C or even above. At 300 ^° C., curing is generally complete in 2 to 5 seconds; at 150 ^° C. it takes about 5 to 15 minutes; at lower temperatures, increasingly longer times are required, for example about 60 minutes at 50 ° C.

Interesting areas of application of the aqueous dispersions of the invention are also-i.a. as an adhesive for flocking Areas with fibers and as a backing for pile fabric to fix the fiber stack on the supporting fabric. Also suitable are the dispersions as adhesives for synthetic fabrics made of paper, Textiles, foam constructions, metal foils, wood veneers, etc. for the production of multilayer packaging materials, insulation materials, wall boards and plywood.

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The aqueous dispersions of the invention are useful for both manufacture of coating layers such as for impregnating material webs. They produce tough, water, organic solvents, household cleaning agents and heat-resistant coating layers of the most varied degrees of hardness and flexibility Adhere firmly to a wide variety of surfaces, such as paper, leather, plastic, steel, aluminum, copper, bronze and other metals.

You can the aqueous dispersions of the invention, the usual additives, such as fillers, pigments, dyes and other auxiliaries customary for adhesives and coating compounds.

Embodiments of the invention are exemplified below described. Parts and percentages are based on weight. The temperatures are given in degrees Celsius. For simplification the methylolated amide condensates are referred to as dimethylol diamide or trimethylol triamide.

A. ^^ fk ^^ ung of a typical emulsion copolymer suitable for carrying out the invention (no patent protection is sought for the polymerization)

Ivian loads a glass reaction vessel in which 554 »0 parts Deionized water are presented and which is kept under a nitrogen atmosphere, with an emulsion of 249.6 parts of ethyl acrylate, 17.1 parts of β-hydroxyethyl methacrylate, 19.0 parts of Triton X-405 (Trade Mark), 1.0 part of 27 percent sodium lauryl sulfate and 113.3 parts deionized water, stir, cool

ο 3

20 and sets 0.40 part of sodium hydrosulfite, 8.0 cnr O, 175 percent solution of ferrous sulfate, .7 HpO, 23.0 cnr one 1. 28 percent solution of potassium persulfate too. As soon as the reaction has reached its peak temperature of about 55 to 60 °, one gives a new batch of monomer emulsion consisting of 499.2 parts of ethyl acrylate, 34.1 parts of β-hydroxymethacrylate, 38.1 parts of Triton X-405, 30 parts of a 27 percent solution of sodium lauryl sulfate, 0.40 parts iiatrium hydrosulfite and 241.3 parts deionized Water, as well as at the same time 77 »0 cnr of a 1.28 per cent solution of potassium persulfate in such a dosage that the temperature is kept at 61 to 63. After the addition is complete, the mixture is stirred

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continue until a decrease in the reaction temperature can be observed. At this point the reaction is accelerated again by adding 0.5 cnr of a 70 percent solution of t-butyl hydroperoxide and 2.0 cnr of a 2.0 percent solution of sodium hydrosulfite. After the final temperature increase brought about by this, stirring is continued until the reaction temperature has again dropped significantly. The dispersion, the latex of the emulsion copolymer, is then cooled to room temperature, its pH value is 2.8, the solids content is 42.8 % and the Brookfield viscosity is 51 cp at room temperature.

B. Preparation of the methylolated polycarboxamides

1. Solution of dimethyl isopthalamide

A mixture of 164.2 parts of isopthalamide is heated with stirring, 405.8 parts of 37 percent aqueous formaldehyde, and 8.5 parts of 90 percent formic acid at reflux temperature of 99 ° C, maintains the reflux for two hours, cools the clear reaction mixture, filtered through a filter and receives a solution of dimethyl isopthalamide with 37 »5% Solid content and pH 3.1 · The product has good water compatibility (more than 500 cm - ^ / 10 g) and is stable.

2. Solution of dimethyloladipamide

Heating a mixture of 144.2 parts of adipamide, 405.8 g 37prozentigen aqueous formaldehyde and 8.5 parts of formic acid for 2.5 hours 90prozentige the reflux temperature of 96-100 ⁰ C, the mixture becomes homogeneous. A clear solution of dimethyloladipamide with a solids content of 4.8% and a pH of 3.4 is obtained by filtering off.

3 · solution of dimethylplsuccinamide

A mixture of 11.6 parts of succinamide, 40.6 parts of 37 percent aqueous formaldehyde and 0.85 parts of 90 percent strength is heated Formic acid on a steam bath for five hours, cools, filtered and obtained a clear solution of dirnethylenesuccinamide.

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4. Solution of dimethyl ο lmal onamid

A mixture of 10.2 parts of malonamide, 40.6 parts, is heated Parts of 37 percent aqueous formaldehyde and 0.85 parts Formic acid on steam bath for three hours until the mixture becomes homogeneous, cools down, filtered and gets a clear Solution of dirnethylmalonamide.

5 · Solution of dimethylol - «* - methylglutaramid _Λ

Heating a mixture of 14.4 parts << - Methylglutaramid and 40.6 parts 37P ^r ozentigen aqueous formaldehyde on a steam bath for 10 minutes long, has occurred until complete dissolution, an hour further heated, filtered to give a clear solution does not fail.

6. Solution of the methylolation product of the trimeric amide of Athylacryla t

The triamide is produced from the hydrogenated trimer of ethyl acrylate by reaction with ammonia under pressure,

For example, at 50 to 70 ⁰ G. heating a mixture of 21.5 parts of this Triamids and 5 ^, 1 parts 37piOzentigen aqueous formaldehyde for one hour on the steam bath until the mixture is homogeneous {, cooled and filtered to give a clear brownish solution of trimethyl oil triamide.

7 · Solution of dirnethylol-o-phthalamide

A mixture of 16.4 parts of o-phthalamide is heated, 40.6 parts of 37 percent aqueous formaldehyde and 0.85 parts of 90 percent formic acid on a three steam bath Hours and receives a clear solution of dirnethylol-o-phthalamide.

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8. Solution of dimethylolsebagamide

A mixture of 20.0 parts of sebazamide, 40.6 parts, is heated Parts of 37 percent aqueous formaldehyde and 0.85 parts of 90 percent formic acid for three hours at reflux temperature and receives a clear solution of the dimethylol sebazamide, which may be used to separate foreign matter can still be filtered.

^ 0 · Preparation of the stabilized copolymer dispersions P of the invention

1. 100 parts of the copolymer latex prepared according to A. are added with 5 parts of the solution of dimethyl isopthalamide prepared according to B. 1. with a solids content of 38.5%.

This mixture can be stored for a long period of one year without gelling or crystallization entry.

This stable dispersion is adjusted to a solids content of 20% , 0.5 part of ammonium chloride is added and the pH is adjusted. The thus prepared extinction is a carded web of viscose fibers with a weight of about 12.5 w g padded, until approximately 11% solids calculated on the fiber weight, is applied. The fiber fleece is then dried at room temperature and heated to 150 ^° C. for 5 minutes for curing.

The consolidated nonwoven fabric can withstand more than 30 washing operations, the same as in a washing machine, without any noticeable impairment with 25 g household detergent in 60 liters of water in the presence of 10 bath towels as ballast will.

2. The same consolidated nonwovens with similar wash strengths are made with the same copolymer latex A produced when the ^ imethylolisopthalamid of example Cl. is successively replaced by:

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8 parts of a 50 percent solution of dimethylol - * - -methylglutarmide,

7 parts of a 30 percent solution of dimethylsuecinamide,

6 parts of a 34.8 percent solution of dimethyloladipamide,

7 parts of a 30 percent solution of dimethylolsebazamide,

4 parts of a 35 percent solution of dimethylolmalonamide,

5 parts of a 34 percent solution of dimethylol-o-phthalamide,

5 parts of an $ 0 percent solution of trimethylolnitrilo- M propionamide, ™

6 parts; a 32 percent solution of trimethylol triamide of the hydrogenated trimer of ethyl acrylate.

100 parts of an aqueous dispersion of 19 »5 parts of an emulsion copolymer of 80% ethyl acrylate, 18 % 2-ethylhexyl acrylate and 2 % methacrylamide, containing 1.3 parts of the emulsifier t-octylphenoxypoly (40) ethoxyethanol, are used to add 5 parts of a 38.5 percent aqueous solution of dimethyl isophthalamide too.

The dispersion obtained in this way can be stored for at least a year without gelling or crystallization occurring.

For processing, 0.5 part of ammonium chloride is added to the dispersion, mixed thoroughly and then the dispersion is padded onto a carded fleece made of viscose fibers with a weight per square meter of approximately 12.5 g until it absorbs 11% solids, calculated on the weight of the fibers, and then dries at room temperature and cures at 150 ^° C. for five minutes.

The nonwoven fabric bonded in this way can withstand at least 10 washing operations of the type indicated above without noticeable damage.

The same results are obtained if, in the same way, a latex of an emusion copolymer of 93% Ethylacrylate and 7% ß-Ureidoäthylmethacrylat works.

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4-. A mixture is prepared from 80.6 parts of the latex of the emulsion copolymer from A., 0.9 parts of methyl cellulose, 8 parts of xylene, 1.6 parts of oxalic acid (10 % solids) and 8.0 parts of an aqueous solution of dimethyl isophthalamide.

This dispersion is spread using a Gardner doctor blade graduated to 0.3 mm Garbadine fabric, which consists of equal parts viscose and acetate fibers, flocked with cut nylon fibers using the usual method, immediately place the fabric on needle frames and heat for 10 minutes at 143 C.

w The flocked fabric thus produced shows excellent dry cleaning and washing strength and a firm hand.

5. Adjust using the method in the previous example flocked fabric using a dispersion of 78.4 parts of a 4-3.0 percent emulsion copolymer Latex of 92.5 mol percent butyl acrylate, and 7 »5 mol percent ß-hydroxyethyl methacrylate, 7 »8 parts of a 38.5 percent aqueous solution of dimethyloladipamide, 1.5 parts of methyl cellulose (Methocel 4-000), 9.9 parts of xylene and 1.5 parts 10 percent oxalic acid.

The flocked fabric has a soft feel, very good wash resistance and good dry cleaning resistance.

The same good results are achieved if one works in the same way with the latex of a copolymer from 50 mole percent methyl acrylate, 4-3 mole percent 2-ethylhexyl acrylate and 7 mole percent N, N'-ethylene urea-N-ethyl vinyl sulfide is working.

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Claims (5)

Dr MEDIGER patent claims: 1. Aqueous impregnation and coating dispersion based on of copolymers of monoathylenically unsaturated monomers, characterized in that they a) an aqueous dispersion of a water-insoluble emulsion copolymer of monoathylenic unsaturated monomers, including 3 to 40 percent by weight at least one monomer containing alcoholic hydroxyl, ureido and / or carboxylamide groups, b) a water-compatible aqueous solution of 1 to 20%, calculated on the weight of the copolymer, of one methylolated polycarboxylic acid amides contains. 2. Dispersion according to claim 1, characterized in that the methylolated amide is water-soluble. 3. Dispersion according to claim 1 or 2, characterized in that the amide is a methylolated isophthalamide, o-phthalamide, Is adipamide, malonamide, succinamide, <x -methylglutaramide. 4. Dispersion according to claim 1 to 3 »characterized in that the aqueous solution is a product of the reaction of a diamide or triamide in acidic aqueous solution at 40 to 100 ⁰ C with at least 1.5 mol of formaldehyde ge nitrogen atom of the amide. 5. Dispersion according to claim 1 to 4, characterized by a Addition of about 0.5 to 2%, calculated on the total weight, of an acidic catalyst. 109837/1270